Process for refining hydrocarbon oils and derivatives



April 1s, 1939.

E. ocoN PROCESS FOR REFINING HYDROCARBON OILS AND DERIVATIVES 2 Sheets-Sheet l Filed March ll, 1957 RW. o.. NESS@ m E. A. ocioN 2,154,820 PROCESS FOR REFINING HYDROCARBON OILS AND DERIVATIVES April 18, 1939.

Filed March ll, 1957 2 Sheets-Sheet 2 1N VENT OR. @W

Patented Apr. 18, 1939 UNITEDv STATES PROCESS -FOR. REFINING HYDROCARBON OILS AND DERIVATIVES l Ernest A. Ocon, New York, N. Y. ApplicationMarch 11, 1937, Serial- No. 130,227

12 Claims. `(Cl. 196-52) This invention relates to heat treatments of bituminous liquids, such as mineral oils, and oxygenated derivatives of the less useful products to recover mainly commercial products such as anti-knock motor fuel and lubricants with a minimum of waste combustion products, and with economy in materials and apparatus'.

An object of this invention is to make possible an efficient cracking of a large proportion of the bituminous liquids as clean distillates, which can be subjected to cracking conditions without much coke formation through the aid of an efficiently formed heating agent, non-oxidizing heat carrier gases, and a contact mass in recovering a larger amount of clean distillates from bituminous liquids, while, at the same time, eliminating inefficient means for supplying heat to the heaviest portions of the bituminous liquids. More specifically, use is made of ysteam and mild oxidizing reactions to recover a larger portion of the initial bituminous liquids as vapors and gaseous products containing high heat energy, and the gaseous products are treated in a way to increase and enhance the products from the cracking of the bituminous distillates.

According to this invention, together with the formation of heat energy from chemical reactions, a recovery is made of additional useful hydrocarbon products by the use of synthesis reactions Which make use of the oxygenated products which according to the invention described,

,are of material value 4in the alkylation zone, the

quenching zone, etc., and which synthesis reactions are very handily provided with reactants from the regeneration of the filtering contact mass used in filtering the distilled residual vapors.

The process will be described by reference to the accompanying drawings, which diagrammatically illustrate the conventional apparatus involved.

In Figure l is shown diagrammatically the means for performing the combined operations.

In Figure 2 is shown more specifically the arrangements in the chambers in which the residual products of the bituminous liquids are treated to release additional `vapors and gaseous products.

In Figure 3 is shown a cross sectional viewA of Figure. 2.

Thecharging stock-of the bituminous liquids, such as crude petroleum oil or topped crude, as from storage I, lis passed through a heat cxchanger 2 and by line 3 into the primary flash tower 5. This initial oil or charge can be preheated to below cracking temperatures or at incipient cracking temperatures in the heat exchanger 2 and other heat exchange units. The preheated charge is injected into the tower 5 by means of a spray device 4, and is subjected 5 to a blast of heated vapors injected through spray device 6, which heated vapors aid in the Vaporization of the charge oil. The vapors arising from the vaporization may then be subjected to fractionation to form oneor a plurality of distillates for cracking and reforming, such as distillates which may be Withdrawn by valved lines 9 and I0. A portion of the unvaporized and condensed products formed in the vaporizing zone of tower 5 are withdrawn by valved line 8 to be 15 passed in heated condition to a flash tower, such as A or -B, preferably through a mild heating coil I2 together with superheated steam or other hydrogenous or non-oxidizing gases, such as hydrogen, normally gaseous paraffin hydrocarbons, steam admixed with reducing gas, carbon monoxide, water gas, producer gas, or inert gasesl such vas nitrogen led in by line I5 and valved line I6.

A plurality of flash treating chambers such as A and B are provided for the distillation of residual oils so that while one of these chambers is being used for distilling the residuals to obtain purified vapors, 'another may be subjected to a regenerationfor removing adsorbed tarry 30 material from the contact mass. .During 4the distillation run in any of such flash distillation chambers some superheated steam may be added to the residual oil heating coil I2 through line I6, and another amount may be added to the bottom of the distilling chamber by means of spray device I8, the total amount of steamA being used being limited to be about 10% by weightA of the oil distilled or less. Residual oil passed through line 5I from the separator zone 93 and/or 40 reflux passed through line 89 from fractionator 6I may be added by means of lines 92 and 34 to the residuals from tower 5 passing to coil I2 through line 8 or be added to the lower part of A tower A or B by lines 5I, 92, 53, 38 or 31. For 45 simplification, three-way valves are shown at 99, 98, 91, 96, 95, 94, 9| and 43 for directing the materials as desired.

' In Figures 2 and Bare shown more detailed views of the construction of the flash distillation chamber, such as A or B, and a cross-sectional view and plan view above the base of the pan 2I.

It is to be understood that the contact mass shown to be located in a basket in the upper parts of the distillation flash chambers may be located in separate chambers connected with the ash distillation chambers, and that each of such contact mass chambers may be provided with means for eiTecting regeneration of the contact mass separately from the distillation chambers.

The oils are flashed alternately into tower A or B by means of line 20 or valved line 31 to a pool of liquids on tray 2|, into which theyr pass tangentially to form a swirling movement. Tray 2| has perforations 28 at the bottom for egress or ingress of materials. Above tray 2| is located bale plate 21 for knocking out tar particles. Below is a grate 26 which may support a coke bed 24. Below coke grate 24 is situated a steam jet I8 into which passes steam from line I5 or junction I1. The bottoms of towers A or B may be tted with removable parts 25 to enable removal of coke. In the upper parts of the towers A and B are provided contact masses 23 for eliminating tarry and other coke forming substances deleterious in pipe stills, said masses being supported by baskets 22. The contact masses may be activated clay, charcoal, broken brick, unglazed clay rings, brick fragments, bauxite, pumice, coke, or other adsorbing mass, which mass may also be coated with metallic or metal oxide catalysts. When towers A or B receive the heated ,residual oils from coil I2 the vapors pass through line 29 or 30 to line 32 or 33 to be introduced into the primary ash tower 5 through spray device 6 to form a blast to aid in the vaporization of the charge oil injected through spray 4. An intermediate condensate of the nature of gas oil is withdrawn from tower 5 by valved line 9 to be cracked in coil I3 at a temperature of about 800 to 950 F., to be subjected under cracking conditions of temperature and pressure for a period of l to 5 minutes with less time as the temperature is increased. A lighter distillate may be withdrawn from tower 5 by valved line ,I0 to be subjected to reforming as in heating tube I4 and a catalytic chamber 92 into which may be injected a mild oxidizing'agent such as steam by line 46. Chamber 92 contains a mild oxidizing catalyst such as oxides of metals in groups 3, 4, 5 and 8 of the periodic system such as copper oxide, chromium oxides, titanium oxide, manganous oxide, tungsten trioxide, vanadium oxides, germanium oxide, silica, chromium sesquioxide, cerium oxide, zeolites containing metals of vthese groups substituted for the alkali or alkaline earth metals or other oxides which retain oxygen to the same extent and the space velocity should be of the order of 10,800 to 600 cu. ft. per hour per cu. ft. of catalyst. Suitable temperatures are from 500J to 900 F. Products from the mild oxidizing chamber 92 are passed through line 41 to cooler 48 under pressure, and thence jointly with the products from cracking coil I3 are passed through line 40 to separation zone 93, passing into a midsection where a `pool of oil is collected on tray 4| perforated with holes `43. Beneath tray 4| is a spray device 42 for injecting gaseous products from towers A or B passed through lines 29, 30 and 33, especially when either of these is undergoing regeneration and producing mainly water gas. Vapor products are led from the separator 93 by line 60 to fractionator tower 6| in which liquids higher boiling than gasoline components are condensed.

Fractionated vapors from 6I are passed by line 10 through a catalytic alkylation zone 1I, thence being joined by overhead vapors led by line I I from tower 5 pass through heat exchanger 2 to coil 12` for condensation. Products of condensation from 12 are received in 13 whence motor fuel liquids are decanted by line 15. Uncondensed products from 13 pass through line 14 to bubble tower 11 to be separated into gases and liquids. Gases passing overhead from 11 comprising carbon monoxide, hydrogen, meth/ane, etc. are withdrawn by line 18, and may be passed through a purifier 19 provided with a reagent for removing sulphurous and carbon dioxide components, such as calcium oxide. The purified gases from 19 are led by line 80 to synthesizing zone 8| in which they may be joined with water gas or products passed through line 33 and 52 from partial combustion in the regeneration of towers A or B. synthesizing zone 8| is provided with a catalyst such as iron or cobalt activated by a weak alkaline oxide, e. g. zinc oxide, or chromic oxide or an alkaline carbonate, cobalt-coppermanganese, which aid in the formation of hydrocarbons. Temperatures of the order of 450 to 600 F., and pressures of about 5 atmospheres and above can be used. The duration or time is controlled to produce the desired types of products.

Any suitable carrier may be used such as magnesia, pumice, diatomaceous earth. Temperatures of about 400 F., pressures of about l0 atmospheres or more and a rate of flow of about 40 litres per hours may be used. In place of iron, nickel gauzev etched by alkaline zinc oxide may be used. Products from the synthesizing zone are passed to a fractionator 83 and may be previously cooled in a cooler 82. The products in 83 are fractionated into an overhead comprising mainly lower alcohols and led out by line 85. Heavy unvaporized synthetic hydrocarbons comprising higher aliphatics may be led by line 81 to be joined with distillate from the primary y tower 5 to be cracked as in cracking coil I3. Overhead vapors from 83 may b'e led to join vapors from 6I passing into alkylation zone 1I to aid in the alkylation. Catalysts which bring about the formation of free radicals, e. g., methyl radicals may be used, such as zinc-chromium, zinc oxide chromates, etc., or catalysts also which aid in forming unsaturated hydrocarbons from the oxygenated hydrocarbons by dehydration,

e. g., alumina, thoria or silica may be used.

These reactions increase and enhance the products while acting to absorb heat.

An intermediate reflux passed through line 84 from 83 may be joined with bottoms of tower 11 withdrawn through line 86 to he used in forming lubricating oil by catalytic polymerization in. Reflux passed through line 62 from 6I contain ing aromatics may also be used in 88 to be subjected to an alkylation.

In separator 13 aqueous condensate solution containing alcohols are passed by line 16 to mix with cracked products entering the separator 93.

Residuals from separator 93 and reflux from .o

6I may be joinedfby line 92 and 34 with residuals from the primary tower 5 entering coil I2 or may be by-passed by lines 35 and 36 to the tower A or B on stream for the vaporization of residual oil from tower 5. Or, residual oil from separator 93 may be passed to the lower part of tower A or B by lines 5I, 53, 31 or 38 when that tower is in use to vaporize residue from tower 5.

Alternately, after either tower A or B has been used in vaporizing residual oil from tower 5 it is` subjected to regeneration by the use of steam passed in through jets I8 with or without the' use of other oxidizing agent under conditions to produce mainly carbon monoxide and hydrogen, at about 1000" C. or less in the coke bed.

4oxygen may be led into the bases of these towers to increase the temperatures during the regeneration.

The exact sizes of apparatus and conditions depend upon the'capacity of the plant, the character of the charging stock, and types of prducts desired. Instruments, valves, pumps, and i other such4 engineering equipment are not all mentioned, but it is understood that they will be used as required and as understood in the art.

It will be understood that the above examples and illustrations are not to be considered. as limitations on the principles of the invention set forth.

Having described my invention, what I claim and desire to secure by Letters Patent, is as follows:

1. A process for treating bituminous oil, which comprises injecting preheated bituminous oil into a flash zone to vaporizea substantial portion. of the oil, passing hot vapors into the ash zone to increase the vaporization of the oil` subjecting a portion of the resulting residues from 'the oil to a steam distillation under substantially cracking conditions, filtering vapor products of said steam distillation through an adsorbent contact mass capable of eliminating deleterious coke forming substances, and using thus ltered vapors as said hot vapors in the flash zone to increase the vaporization of the bituminous oil.

2. A process for treating crude petroleum oils, which comprises injecting a heated crude oil into a iiash zone to vaporizev a substantial portion of the oil, passing hot vapors into .the flash zone to increase the amount of vapors, subjecting a portion of resultant residues from. the iiash zone to distillation in the presence of a non-.oxidizing gaseous agent, filtering vapors from the residue distillation through an adsorbent contact mass to eliminate deleterious coke forming substances, and using thus filtered vapors as said hot vapors in the flash zone to increase the amount of "vapors 3. A process for treating bituminous oil and derivatives, which comprises subjecting a bitumicontaining lower alcohols and hydrocarbons, andv passing the separated gases and-vapors to a catalytic alkylation zone where vapor products of the cracking are subjected to'an alkylation, fractionating products from the alkylation zone to recover condensates and a gaseous material largely composed of carbon monoxide and hY- drogen, subjecting such gaseous material to a synthesizing hydrogenation of the carbon monoxide to form oxygenated hydrocarbon derivatives and hydrocarbons, fractionating the syn-v thesized products to obtain a gaseous mixture using such gaseous mixture in the alkylation.

4. A process for treating hydrocarbon oils and derivatives, which comprises subjecting oils to cracking under conditions to produce lower boiling products and tarry substances, separating vapors from tarry substances thus produced, filteringv the vapors through an adsorbent contact mass upon which tarry substances become deposited. subjecting such tarry substances to oxidation under conditions adequate to produce a gaseous mixture containing carbon monoxidev and hydrogen, subjecting carbon monoxide and hydrogen from the gaseous mixture to a synthesizing reaction to produce hydrocarbons and oxygenated hydrocarbon derivatives, and reacting such products of the synthesis with lower boiling products from the cracking in the presence of a catalyst to cause alkylation of the products from the cracking.

' 5. A process for treating hydrocarbon oils and derivatives, which comprises subjecting a hydrocarbon oil to cracking to form gasoline vapors, separating liquids higher boiling than gasoline from vapor products of the cracking, subjecting such vapor products to a catalytic alkylation in the vapor phase with a catalyst capable of decomposing oxygenated and hydrocarbon derivatives, fractionating products of the alkylation to recover condensates and gaseous material composed largely of carbon monoxide and hydrogen, subjecting such gaseous material to a synthesizing hydrogenation of carbon monoxide to produce oxygenated hydrocarbon derivatives and hydrccarbons, fractionating the synthesized products to obtain a gaseous mixture containing unreacted carbon monoxide, hydrogen, lower alcohols and hydrocarbons, and using such la gaseous mixture in the alkylation.

6. A process for treating bituminous oil, which comprises injecting'bituminous oil into a-ash zone to vaporize. a substantial fraction' of the oil, passing hot vapors into the flash zone to increase the vaporization of the cil, collecting a distillate from the vapors thus produced, s ubjecting said distillate to cracking to produce gasoline, separating liquids higher boiling than gasoline from vapor products of the cracking, subjecting thus separated liquid products of the cracking to a distillation, filtering vapors released by the distillation through an adsorbent contact mass capable of eliminating deleterious coke forming substances, and using thus filtered vapors as said hot vapors passed into the flash zone to increase the vaporization of the initial oil.

7. A process in accordance with claim 5, in which a normally gaseous fraction comprising oleiinsY are collected as a condensate recovered from products of the alkylation and are combined with a low boiling condensate fractionated from the synthesized products, and said mixture is subjected to a polymerizing reaction to produce lubricants.

8. A process in accordance with claim 5, in which liquids higher boiling than gasoline separated from the cracked products are subjected to polymerization with oleins such as recovered in the fractionation of the alkylated products and the synthesized products.

9. A process in accordance with claim 5, in

gasoline, mixing said condensate While hot with the hot steam cracked products of the residual oil, filtering the resulting vapor products of the mixture for elimination of tar 'forming substances, and passing the ltered deleterious gum and distillation are ycontacted with the products of the oxidizing reaction.

12. Apparatus for the separation of vapor from liquids comprising a tower, a liquid pool retaining means disposed substantially above the botl tom of said tower for maintaining constantly a substantial pool of liquid in circulatory turbulent motion, a plurality of ports in said retaining means arranged to control a ow'of a portion of said 'substantial pool of liquid from said retaining means to the bottom of said tower and to control the period of time said portion of liquid is maintained in the turbulent pool to secure the utmost Vaporization and separation of low boiling point fractions from liquids, and means for continuously injecting into the liquid on said liquid retaining means a hot fluid comprising mainly of vapor and liquid in such a manner to impart the circulatory turbulent motion to the liquid pool in said retaining means and to continuously replace said portion of liquid flowing constantly 'to the bottom of said tower.

ERNEST A. OCON. 

